JP2012145481A - Method for testing heat resistance of aliphatic terminal diol and method for producing thermoplastic resin by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistance testing method for evaluating a color tone of a molten substance of an aliphatic terminal diol material including an aromatic for obtaining a thermoplastic resin with a good color tone and a method for producing a thermoplastic resin by using the same.SOLUTION: A heat resistance testing method for aliphatic terminal diol represented by general formula (I) comprises a step of evaluating a color tone of a molten substance of a mixture of the aliphatic terminal diol represented by general formula (I) and aromatic carbonic acid diester in a weight ratio of 3:2 to 5:1 attained after keeping the mixture in the atmosphere in a molten state of 150 to 320°C for 10 to 150 minutes.

Description

  The present invention relates to a test method for producing a thermoplastic resin excellent in hue using an aliphatic terminal diol having a specific structure as a raw material, and a production method using the same.

  Polycarbonate resins obtained from interfacial polycondensation of bisphenol A and phosgene are widely used for various applications because of their excellent mechanical and thermal properties. However, the polycarbonate made of bisphenol A has problems that the fluidity is insufficient and the birefringence of the molded product is large.

Patent Document 1 discloses a resin using an aliphatic terminal diol such as hexanediol or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene.
However, polycarbonate resin obtained by melt polymerization usually undergoes polycondensation while being heated to a temperature of 250 to 330 ° C., so that it is possible to obtain a product with excellent quality such as deterioration of color tone due to long-term heat history at high temperature. It was difficult.

  Patent Document 2 discloses a molten Hazen after holding a 1: 1 part by weight mixture of an aromatic dihydroxy compound and a carbonic diester in an atmosphere at 175 ° C. for 5 hours in the atmosphere in an aromatic diol having a hydroxyl group directly bonded to an aromatic ring. A method for producing an aromatic polycarbonate using an aromatic dihydroxy compound and a carbonic acid diester having a color number of 40 or less is disclosed.

  Furthermore, Patent Document 3 discloses that an aromatic dihydroxy compound and a carbonic acid diester are produced when an aromatic carbonic acid diester, a dihydroxy compound having an alicyclic structure, and an aromatic-aliphatic copolymer polycarbonate using an aromatic dihydroxy compound as a raw material are produced. A method for producing an aromatic polycarbonate using an aromatic dihydroxy compound having a melt Hazen color number of No. 50 or less after holding a mixture having a weight ratio of 1: 1 in the atmosphere at 260 ° C. for 3 hours is disclosed.

  However, with aliphatic-terminated diol raw materials containing aromatics to obtain a thermoplastic resin with excellent hue, it is difficult to discriminate even when trying these prior art test methods, and a heat resistance test method for efficiently evaluating the molten hue and A method for producing a thermoplastic resin excellent in hue used has not yet been provided.

JP-A-10-101786 JP-A-9-52947 JP 2002-317043 A

  An object of the present invention is to solve the above-mentioned problems, and a heat resistance test method for evaluating a molten hue of an aliphatic terminal diol raw material containing an aromatic to obtain a thermoplastic resin having an excellent hue, and using the same It is to provide a method for producing a thermoplastic resin.

  The inventor performs a melt test on a mixed melt of an aliphatic terminal diol having a specific structure and a carbonic acid diester at a specific ratio, a specific temperature condition, and a specific melt holding time, so that the by-produced phenol and impurities in the raw material It discovered that it acted and colored, and it discovered that the thermoplastic resin excellent in a hue was obtained by using the raw material whose melt APHA of the said mixed melt is below a specific value, and came to complete this invention.

（式（Ｉ）中Ｒ１、Ｒ２はそれぞれ独立に炭素数１〜５のアルキル基または炭素数１〜５のアルコキシル基、Ｒ３〜Ｒ６はそれぞれ独立に水素原子、アルキル基、アルコキシル基、シクロアルキル基、シクロアルコキシル基、アリール基またはアリールオキシ基、Ａ１は単結合、アルキル基、アルコキシル基、シクロアルキル基、シクロアルコキシル基、アリール基またはアリールオキシ基である。）
２．上記一般式（Ｉ）のＡ１がフルオレン環であることを特徴とする上記１記載の耐熱性の試験方法。
３．上記一般式（Ｉ）が９，９−ビス［４−（２−ヒドロキシエトキシ）フェニル］フルオレンであることを特徴とする上記１又は、２記載の耐熱性の試験方法。
４．芳香族炭酸ジエステルがジフェニルカーボネートであることを特徴とする上記１〜３のいずれかに記載の耐熱性の試験方法。
５．上記一般式（Ｉ）で表わされる脂肪族末端ジオールを加熱溶融下、重合せしめる熱可塑性樹脂の製造方法であって
（Ａ）：脂肪族末端ジオールに対して耐熱性試験をする工程
（Ｂ）：上記（Ａ）工程で得られた耐熱性の試験結果に基づき、脂肪族末端ジオールと芳香族炭酸ジエステルの重量比２：１の混合物を大気中２７０℃で３０分保持後の溶融ＡＰＨＡに換算したとき、溶融ＡＰＨＡが３００番以下である脂肪族末端ジオールを良品として選別する工程
（Ｃ）：上記（Ｂ）工程で良品として選別した脂肪族末端ジオールを用いて溶融重合を行う工程
を経ることを特徴とする熱可塑性樹脂の製造方法。
６．上記脂肪族末端ジオールが９，９−ビス［４−（２−ヒドロキシエトキシ）フェニル］フルオレン及びジフェニルカーボネートを用いることを特徴とする上記５に記載の熱可塑性樹脂の製造方法。
７．熱可塑性樹脂が、ポリカーボネート、ポリエステルカーボネート、ポリエステルからなる群より選ばれる少なくとも１種であることを特徴とする上記５または６のいずれかに記載の製造方法。 That is, the present invention is 1. A mixture of an aliphatic terminal diol represented by the following general formula (I) (hereinafter sometimes simply referred to as an aliphatic terminal diol) and an aromatic carbonic acid diester in a weight ratio of 3: 2 to 5: 1 is A method for testing the heat resistance of an aliphatic terminal diol represented by the general formula (I), wherein the molten hue after being held for 10 to 150 minutes in a molten state at 320 ° C. is evaluated.

(In formula (I), R1 and R2 are each independently an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms, and R3 to R6 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, and a cycloalkyl group. , Cycloalkoxyl group, aryl group or aryloxy group, A1 is a single bond, alkyl group, alkoxyl group, cycloalkyl group, cycloalkoxyl group, aryl group or aryloxy group.
2. 2. The heat resistance test method according to 1 above, wherein A1 in the general formula (I) is a fluorene ring.
3. 3. The heat resistance test method according to 1 or 2 above, wherein the general formula (I) is 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene.
4). 4. The heat resistance test method according to any one of 1 to 3 above, wherein the aromatic carbonic acid diester is diphenyl carbonate.
5. A method for producing a thermoplastic resin in which an aliphatic terminal diol represented by the above general formula (I) is polymerized by heating and melting, and (A): a step of performing a heat resistance test on the aliphatic terminal diol (B): Based on the heat resistance test results obtained in the above step (A), a mixture of an aliphatic terminal diol and an aromatic carbonic acid diester in a weight ratio of 2: 1 was converted to molten APHA after being kept in the atmosphere at 270 ° C. for 30 minutes. Step (C) of selecting an aliphatic terminal diol having a melted APHA of 300 or less as a non-defective product: A step of performing melt polymerization using the aliphatic terminal diol selected as a non-defective product in the step (B). A method for producing a thermoplastic resin.
6). 6. The method for producing a thermoplastic resin as described in 5 above, wherein the aliphatic terminal diol is 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and diphenyl carbonate.
7). 7. The method according to any one of 5 or 6 above, wherein the thermoplastic resin is at least one selected from the group consisting of polycarbonate, polyester carbonate, and polyester.

  According to the present invention, a thermoplastic resin having a very good hue can be efficiently produced, and the obtained thermoplastic resin can be suitably used for plastic optical materials such as various lenses, prisms, optical disk substrates, and optical films.

(Test method for heat resistance of aliphatic terminal diol)
The present invention relates to an aliphatic terminal characterized by evaluating a molten hue by defining a weight ratio of an aliphatic terminal diol represented by the general formula (I) and an aromatic carbonic diester, a temperature range, and a melting retention time. This is a test method for heat resistance of diol.

  That is, the heating temperature in the test method of the present invention is 150 to 320 ° C. Preferably, it is 200-300 degreeC, More preferably, it is 250-300 degreeC. When the heating temperature is lower than 150 ° C., the generation of phenol is extremely small and the hue change is small. On the other hand, when the temperature is higher than 320 ° C., the coloring is quick and the reproducibility cannot be obtained and the control becomes impossible.

  The heating time in the test method of the present invention is 10 to 150 minutes. The heating time can be appropriately changed depending on the heating temperature and the measurement sample amount, but is preferably 10 to 80 minutes, more preferably 15 to 60 minutes. When the heating time is shorter than 10 minutes, the change in hue becomes small, and the quality of the raw material cannot be discriminated. On the other hand, when it is longer than 150 minutes, coloring becomes large and it is impossible to determine whether the raw material is good or bad.

  In the test method of the present invention, the weight ratio of the aliphatic terminal diol to the aromatic carbonic acid diester is 3: 2 to 5: 1. A mixture of 2: 1 to 4: 1 is preferable, and a mixture of 2: 1 to 3: 1 is more preferable. In the weight ratio of the aliphatic terminal diol and the aromatic carbonic acid diester, when the proportion of the aliphatic terminal diol is excessively large, the amount of generated phenol is too small, and there is little change in coloring, and it is impossible to select good products. On the other hand, when the proportion of the aliphatic terminal diol is excessively small in the weight ratio between the aliphatic terminal diol and the aromatic carbonic acid diester, coloring due to the generated phenol is large and it is difficult to determine whether the raw material is good or bad. Moreover, there is also a problem that the viscosity increases due to the progress of the polymerization, making it difficult to evaluate the hue.

  The aliphatic terminal diol in the present invention is an aliphatic terminal diol represented by the general formula (I), and in the formula (I), R 1 and R 2 are each independently an alkyl group having 1 to 5 carbon atoms or 1 carbon atom. To 5 alkoxyl groups, R3 to R6 are each independently a hydrogen atom, alkyl group, alkoxyl group, cycloalkyl group, cycloalkoxyl group, aryl group or aryloxy group, A1 is a single bond, alkyl group, alkoxyl group, cycloalkyl Group, cycloalkoxyl group, aryl group or aryloxy group. Specifically, 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxyethoxy) phenyl) butane, 2,2-bis (4- ( 2-hydroxyethoxy) phenyl) octane, bis (4- (2-hydroxyethoxy) phenyl) phenylmethane, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxy Ethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9 Resins obtained by mentioning 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, etc. 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is preferred from the standpoint of the optical properties. You may use these individually or in combination of 2 or more types.

  The thermoplastic resin in the present invention may be copolymerized with an aliphatic terminal diol and other copolymer components. Examples of the copolymer component include a diol component and a dicarboxylic acid component. Examples of the diol component other than the aliphatic terminal diol include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3-methylphenyl). Propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydibiphenyl, 3,3 ′, 5 , 5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9- Bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene and the like can be mentioned. You may use these individually or in combination of 2 or more types.

  Dicarboxylic acid components include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, anthracene dicarboxylic acid, aromatic dicarboxylic acid such as phenanthrene dicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Aliphatic dicarboxylic acids such as methylmalonic acid and ethylmalonic acid, biphenyldicarboxylic acids such as 2,2′-biphenyldicarboxylic acid, aliphatic dicarboxylic acids such as 1,4-cyclodicarboxylic acid and 2,6-decalindicarboxylic acid Etc. You may use these individually or in combination of 2 or more types. In addition, acid chlorides and esters are used as these derivatives.

(Method for producing thermoplastic resin with excellent hue)
In the present invention, when a thermoplastic resin is produced by heat-melting and polycondensing a raw material containing at least an aliphatic terminal diol, the mixture of the aliphatic terminal diol and the aromatic carbonic diester is maintained in the atmosphere at a temperature equal to or higher than the melting point for a certain period of time. This is a method for producing a thermoplastic resin using an aliphatic terminal diol and an aromatic carbonic acid diester selected by a test method for evaluating a later molten hue.

  That is, in the present invention, when the heat resistance test described above was performed and a 2: 1 part by weight mixture of an aliphatic terminal diol and an aromatic carbonic acid diester was converted to molten APHA after being held at 270 ° C. for 30 minutes in the atmosphere, An aliphatic terminal diol having a value of 300 or less, preferably 200 or less, particularly preferably 100 or less is used as the aromatic carbonic acid diester. When the heat resistance and heat resistance test is performed using an aliphatic terminal diol having an APHA higher than 300 as the aromatic carbonic acid diester, the pellet hue obtained is deteriorated.

  In the present invention, molten APHA is measured by the method described in JIS K-0071. In addition, regarding molten APHA, it is preferable to use the value at the time of melt | dissolving the aliphatic terminal diol: 3.0g and aromatic carbonate diester: 1.5g for the sample amount to fuse | melt.

  Examples of the aromatic carbonic acid diester in the present invention include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, and the like, among which diphenyl carbonate is preferable.

  One embodiment of the production method of the present invention is a method for producing a polycarbonate resin. In the present embodiment, a composition containing a diol component containing at least an aliphatic terminal diol, a carbonic acid diester component, and a catalyst such as a basic compound catalyst, a transesterification catalyst, and a mixed catalyst composed of both is used. In this embodiment, a diol component and a carbonic acid diester component react in the presence of a catalyst to produce a polycarbonate resin.

Each of the diol components used in the present embodiment may be a single component, or the dihydroxy component may contain two or more compounds, that is, may contain a copolymer component.
In addition, it is preferable that diphenyl carbonate is used in the ratio of about 0.90-1.15 mol with respect to the total 1 mol of a diol component, More preferably, it is a ratio of about 0.95-1.05 mol.

  When 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter abbreviated as BPEF) is used in the polycarbonate resin production method of the present embodiment, the content is based on the number of moles of the diol component. Preferably it is 50 mol% or more, More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more. By using BPEF in the above range, a polycarbonate having more excellent hue and optical properties can be produced.

  In the method for producing a polycarbonate resin of the present embodiment, a polymerization catalyst can be used for promoting the reaction. As such a polymerization catalyst, it is preferable to use an alkali metal compound, an alkaline earth metal compound or a transition metal compound as a main component, and if necessary, further use a nitrogen-containing basic compound as a subsidiary component.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, stearic acid. Examples include sodium, potassium stearate, lithium stearate, sodium salt of bisphenol A, potassium salt, lithium salt, sodium benzoate, potassium benzoate, lithium benzoate and the like.

  Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, carbonate Examples include strontium, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

  Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine, and the like. .

  Other transesterification catalysts include zinc, tin, zirconium, lead, titanium, germanium, antimony, and osmium salts. For example, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, Zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate titanium tetrabutoxide (IV), titanium tetraisopropoxide, titanium (IV) = tetrakis (2-ethyl-1- Hexanolate), titanium oxide, tris (2,4-pentadionate) aluminum (III) and the like.

These catalysts may be used alone or in combination of two or more. The amount of these catalysts is the total 1 mol of the diol component, preferably 1 × ¹⁰ -9 ~1 × ^{10 -3} mol, more preferably in a ratio of 1 × ¹⁰ -7 ~1 × ^{10 -3} mol Used.

The method for producing a polycarbonate resin of the present embodiment can be produced by transesterifying a diol component and a carbonic acid diester (transesterification method).
In the transesterification method, the diol component and bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours.

  After completion of the polymerization reaction, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known acidic substance is preferably performed. Examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, and phosphorous acid. Phosphoric acids such as phosphoric acid and phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, Phosphorous esters such as di-n-hexyl phosphate, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, monophosphate Phosphate esters such as octyl, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, phenyl Phosphonic acid esters such as diethyl sulfonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, and aromatic sulfonic acids such as tetrabutylphosphonium dodecylbenzenesulfonate Examples thereof include organic halides such as salts, stearic acid chloride, benzoyl chloride and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride. These deactivators are preferably used in an amount of 0.01 to 50 times mol, more preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable. After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 320 ° C may be provided.

  Another embodiment of the present invention is a method for producing a polyester carbonate resin. In this embodiment, a composition containing a diol component containing at least an aliphatic terminal diol, a dicarboxylic acid component, a carbonic acid diester component, and a catalyst such as a basic compound catalyst, a transesterification catalyst, and a mixed catalyst composed of both is used. . In this embodiment, a diol component, a carbonic acid diester component, and a dicarboxylic acid component react in the presence of a catalyst to produce a polyester carbonate resin.

Each of the diol component and the dicarboxylic acid component used in this embodiment may be a single component or may contain two or more components.
In the method for producing a polyester carbonate resin of the present embodiment, when BPEF is used as the diol component, the content thereof is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably, based on the number of moles of the diol component. Is 80 mol% or more. By using BPEF in the above range, it is possible to produce a polyester carbonate that is more excellent in hue and optical properties.

  In the method for producing the polyester carbonate resin of the present embodiment, a polymerization catalyst can be used for promoting the reaction. As such a polymerization catalyst, it is preferable to use an alkali metal compound, an alkaline earth metal compound or a transition metal compound as a main component, and if necessary, further use a nitrogen-containing basic compound as a subsidiary component.

Specific examples of the alkali metal compound, alkaline earth metal compound, and nitrogen-containing basic compound are the same as those described in the method for producing the polycarbonate resin.
These catalysts may be used alone or in combination of two or more. The amount of these catalysts is the total 1 mol of the diol component, preferably 1 × ¹⁰ -9 ~1 × ^{10 -3} mol, more preferably in a ratio of 1 × ¹⁰ -7 ~1 × ^{10 -3} mol Used.

  The production method of the polyester carbonate resin of the present embodiment can be produced by transesterifying a diol component, a dicarboxylic acid component and a carbonic acid diester (transesterification method).

  In the transesterification method, a diol component, a dicarboxylic acid component, and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours.

  After completion of the polymerization reaction, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known acidic substance is preferably performed. Examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, and phosphorous acid. Phosphoric acids such as phosphoric acid and phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, Phosphorous esters such as di-n-hexyl phosphate, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, monophosphate Phosphate esters such as octyl, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, phenyl Phosphonic acid esters such as diethyl sulfonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, and aromatic sulfonic acids such as tetrabutylphosphonium dodecylbenzenesulfonate Examples thereof include organic halides such as salts, stearic acid chloride, benzoyl chloride and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride. These deactivators are preferably used in an amount of 0.01 to 50 times mol, more preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable. After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 320 ° C may be provided.

  Another embodiment of the present invention is a method for producing a polyester resin. In this embodiment, a diol component containing at least an aliphatic terminal diol and a dicarboxylic acid component react to produce a polyester resin.

  The diol component and the dicarboxylic acid component used in the present embodiment may each be a single component, or the diol component and / or the dicarboxylic acid component may contain two or more compounds.

  In the method for producing a polyester resin according to this embodiment, when BPEF is used, the content thereof is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol%, based on the number of moles of the diol component. That's it. By using BPEF in the above range, a polyester having more excellent hue and optical properties can be produced.

  In the method for producing a polyester resin of the present embodiment, a polymerization catalyst can be used for promoting the reaction. As such a polymerization catalyst, an alkali metal compound, an alkaline earth metal compound or a transition metal compound is preferably used as a main component. As specific alkali metal compounds and alkaline earth metal compounds, compounds similar to those described in the above-described method for producing a polycarbonate resin can be used. Moreover, as a specific transition metal compound, the compound illustrated with the other transesterification catalyst demonstrated with the manufacturing method of the above-mentioned polycarbonate resin can be used.

These catalysts may be used alone or in combination of two or more. The amount of these catalysts is the total 1 mol of the diol component, preferably 1 × ¹⁰ -9 ~1 × ^{10 -3} mol, more preferably in a ratio of 1 × ¹⁰ -7 ~1 × ^{10 -3} mol Used.

  The polyester resin production method of the present embodiment can be produced by subjecting a diol component and a dicarboxylic acid component to an esterification reaction or a transesterification reaction, and further a polycondensation reaction.

  In the esterification reaction or transesterification reaction, first, the first stage reaction is carried out at a temperature of 120 to 220 ° C., preferably 160 to 200 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. The reaction is carried out at a pressure of ~ 200 Torr. Next, the temperature is gradually raised to the final temperature of 230 to 260 ° C. over 1 to 3 hours, and the pressure is gradually reduced to 1 Torr or less of the final pressure, and the reaction is continued. Finally, the polycondensation reaction proceeds at a temperature of 230 to 260 ° C. under a reduced pressure of 1 Torr or less, and when the viscosity reaches a predetermined viscosity, the pressure is restored with nitrogen to complete the reaction. The reaction time of 1 Torr or less is 0.1 to 2 hours, and the total reaction time is 1 to 6 hours, usually 2 to 5 hours.

  By the way, the thermoplastic resin obtained by the production method of the present invention is obtained by dissolving 0.35 g of the polymer in 50 cc of methylene chloride and having a specific viscosity measured at 20 ° C. in the range of 0.12 to 0.55. Preferably, it is more preferable in the range of 0.15 to 0.45. A specific viscosity of less than 0.12 is not preferable because the molded product becomes brittle. If the specific viscosity is higher than 0.55, the polymerization time becomes longer, the hue of the resin becomes worse, the melt viscosity becomes higher, and the moldability becomes worse.

  In the thermoplastic resin obtained by the production method of the present invention, the b value of the pellet obtained after polymerization is -8.0 to 8.0, preferably -7.0 to 7.0, more preferably -5.0 to A range of 5.0 is preferred. If the pellet b value is outside the above range, an optical component with good hue cannot be obtained, which is not preferable.

The thermoplastic resin obtained by the production method of the present invention has a solution b value of −5.0 to 5.0, preferably −3.0 to 3.3 when 1 g of pellets obtained after polymerization is dissolved in 5 ml of methylene chloride. It is preferably 0, more preferably in the range of -1.0 to 1.0. If the solution b value is out of the above range, an optical component with good hue cannot be obtained.
According to the present invention, since the aliphatic terminal diol to be used can be selected by a heat resistance test, a resin excellent in such hue can be produced more efficiently.

  The thermoplastic resin obtained by the production method of the present invention is not particularly limited in a method for adding various additives to the polycondensation product and adding it as a composition. For example, these may be added while the thermoplastic resin as a reaction product is in a molten state, or may be added after being re-melted after pelletizing the thermoplastic resin. Specific examples of the additive include a mold release agent, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

Hereinafter, various additives will be described.
As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester, partial ester or total ester of polyhydric alcohol and fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

  Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like. Stearyl stearate is preferred.

As partial ester or total ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, All or partial esters of dipentaerythritol such as pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. Can be mentioned. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.

The content of the release agent in the thermoplastic resin in the present invention is preferably in the range of 0.005 to 2.0 parts by weight, and in the range of 0.01 to 0.6 parts by weight with respect to 100 parts by weight of the obtained resin. Is more preferable, and the range of 0.02 to 0.5 parts by weight is further preferable.
Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.

  Examples of phosphorus heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite Phyto, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bi (Nonylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite Phosphite, Tributyl phosphate, Triethyl phosphate, Trimethyl phosphate, Triphenyl phosphate, Diphenyl monoorthoxenyl phosphate, Dibutyl phosphate, Dioctyl phosphate, Diisopropyl phosphate, Dimethyl benzenephosphonate, Diethylbenzenephosphonate, Dipropylbenzenephosphonate, Tetrakis (2 , 4-Di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl) Ruphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) Examples include -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite.

  Among them, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-) tert-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3 ′ -Biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphospho Knight and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite are used. Particular preference is given to using bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

The content of the phosphorus-based heat stabilizer in the thermoplastic resin in the present invention is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the obtained resin.
As the sulfur-based heat stabilizer, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), Examples include dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thiodipropionate, distearyl-3, 3′-thiodipropionate. Among them, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thio Dipropionate is preferred. Particularly preferred is pentaerythritol-tetrakis (3-laurylthiopropionate). The thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), and the like, and can be easily used.

As for content of the sulfur type heat stabilizer in the thermoplastic resin in this invention, 0.001-0.2 weight part is preferable with respect to 100 weight part of resin obtained.
Examples of the hindered phenol heat stabilizer include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1- And dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane. . Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferably used.

The content of the hindered phenol heat stabilizer in the thermoplastic resin in the present invention is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the obtained resin.
Examples of the ultraviolet absorber include at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imino ester ultraviolet absorbers, and cyanoacrylates. preferable.

  Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy- 3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy 3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3- Benzoxazin-4-one), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole. These can be used alone or in a mixture of two or more.

  Preferably, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumyl) Phenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole And more preferably 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2 ′ Methylenebis [4- (1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol].

  Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- Methoxyphenyl) meta , 2-hydroxy -4-n-dodecyloxy benzoin phenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone.

  Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-bis ( And 2.4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol.

  Examples of cyclic imino ester UV absorbers include 2,2′-bis (3,1-benzoxazin-4-one) and 2,2′-p-phenylenebis (3,1-benzoxazin-4-one). 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) bis (3,1-benzoxazin-4-one) ), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-nitro-p-phenylene) bis (3,1- Benzoxazin-4-one) and 2,2 ′-(2-chloro-p-ph) Ylene) bis (3,1-benzoxazin-4-one) is illustrated.

  Among them, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred. In particular, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one) is preferred. Such a compound is commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and can be easily used.

  As the cyanoacrylate ultraviolet absorber, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenyl) Examples include acryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, still more preferably 100 parts by weight of the obtained resin. 0.05 to 0.8 part by weight. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance to the molded object obtained according to a use.

Examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant. The bluing agent is effective for eliminating the yellow color of the copolymer. In particular, in the case of a copolymer imparted with weather resistance, since a certain amount of UV absorber is blended, there is a reality that the molded body tends to be yellowish depending on the action and color of the UV absorber, especially in sheets and lenses. In order to give a natural transparency, blending of a bluing agent is very effective.
The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm based on the copolymer.

The following examples further illustrate the present invention. The evaluation was based on the following method.
(1) Hazen color number (APHA): Based on the color number test method shown in JIS K-0071, a colorimetric tube having a diameter of 25 mm and a wall thickness of 1.5 mm is used. Measurements were made in comparison with Hazen standard colorimetric solution. Moreover, the aluminum ingot hot bath shown by JIS K-0071 was also used for the melting apparatus, and this was also used for maintaining the molten state.

(2) Specific viscosity: The pellet obtained after the completion of polymerization was dried at 120 ° C. for 4 hours, and a solution in which 0.35 g of the pellet was dissolved in 50 cc of methylene chloride was used as a measurement sample. In the measurement, the passage time between the marked lines of the Oswald viscosity tube was measured in a constant temperature bath of 20 ± 0.01 ° C., and the specific viscosity (η _sp ) of the solution at 20 ° C. was obtained from the following formula.
η _sp = (t ₁ −t ₀ ) / t ₀
Here, the specific viscosity t _{1 is the} passage time between the marked lines of the polymer solution, and t ₀ is the passage time between the marked lines of methylene chloride.

(3) Pellet b value: The thermoplastic resin pellet obtained after completion of the polymerization (the pellet shape is 4 mm in length and about 1 to 2 mm in diameter) is put in a glass cell, and the pellet hue using a Nippon Denshoku color difference meter SE-2000 Was measured.

(Synthesis Example 1)
A glass reactor equipped with a stirrer, a condenser tube and a burette was charged with 350 g (1.94 mol) of fluorenone and 1070 g (7.78 mol) of phenoxyethanol, and 2.3 g of β-mercaptopropionic acid was added to the stirred mixture. While maintaining the reaction temperature at 50 ° C., 570 g of 98% by weight sulfuric acid was added dropwise over 60 minutes. After completion of the dropwise addition, the reaction temperature was kept at 50 ° C., and the reaction was completed by further stirring for 5 hours.
After completion of the reaction, 920 g of a 48 wt% aqueous sodium hydroxide solution was added dropwise to the reaction mixture while maintaining the temperature at 80 ° C. The pH after the completion of dropping was about 8. 2.5 kg of methanol was added and cooled to 10 ° C. to precipitate a solid. After removing the solid matter by filtration, 3.5 kg of toluene and 1.0 kg of water were added and heated to 85 ° C. to dissolve sodium sulfate. After removing the aqueous phase, the organic phase was further washed three times with 85 ° C. water. By cooling the toluene phase to 10 ° C., 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was obtained. Then, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was completely dissolved in acetone, activated carbon (NoritSX Plus) was added, and the mixture was stirred for 1 hour. Thereafter, the activated carbon was filtered and acetone was distilled off to obtain 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter sometimes abbreviated as BPEF-1).

(Synthesis Example 2)
A glass reactor equipped with a stirrer, a condenser tube and a burette was charged with 350 g (1.94 mol) of fluorenone and 1070 g (7.78 mol) of phenoxyethanol, and 2.3 g of β-mercaptopropionic acid was added to the stirred mixture. While maintaining the reaction temperature at 50 ° C., 570 g of 98% by weight sulfuric acid was added dropwise over 60 minutes. After completion of the dropwise addition, the reaction temperature was kept at 50 ° C., and the reaction was completed by further stirring for 5 hours.
After completion of the reaction, 920 g of a 48 wt% aqueous sodium hydroxide solution was added dropwise to the reaction mixture while maintaining the temperature at 80 ° C. The pH after the completion of dropping was about 8. 2.5 kg of methanol was added and cooled to 10 ° C. to precipitate a solid. After removing the solid matter by filtration, 3.5 kg of toluene and 1.0 kg of water were added and heated to 85 ° C. to dissolve sodium sulfate. After removing the aqueous phase, the organic phase was further washed once with 85 ° C. water. By cooling the toluene phase to 10 ° C., 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter sometimes abbreviated as BPEF-2) was obtained.

Example 1
(Melting test 1-1)
BPEF-1: 3.0 g, diphenyl carbonate (hereinafter sometimes abbreviated as DPC): 1.5 g was kept in the atmosphere at 270 ° C. for 30 minutes. The Hazen color number of the mixed melt was 200.
(Melting test 1-2)
BPEF-2: 3.0 g and DPC: 1.5 g were kept in the atmosphere at 270 ° C. for 30 minutes. The Hazen color number of the mixed melt was 400.

(Synthesis 1-1) Resin A
Using the above BPEF-1 and DPC, BPEF 149.09 parts by weight, DPC 87.40 parts by weight, bisphenol A (hereinafter sometimes abbreviated as BPA) 13.68 g, sodium hydrogen carbonate 1.01 × 10 ⁻³ parts by weight Was placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under normal pressure of nitrogen atmosphere, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 kPa over 20 minutes, and the temperature was increased to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 0.13 kPa or less over 90 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 0.13 kPa or less. Thereafter, the produced polycarbonate copolymer was extracted while pelletizing. The polycarbonate had a specific viscosity of 0.202 and a pellet b value of 3.9.

(Synthesis 1-2) Resin A
A polycarbonate pellet was obtained in the same manner as in Synthesis 1-1 except that BPEF-1 in Synthesis 1-1 was changed to BPEF-2. The polycarbonate had a specific viscosity of 0.212 and a pellet b value of 9.8.

(Synthesis 1-3) Resin B
Using the above BPEF-1 and DPC, BPEF 140.32 parts by weight, DPC 54.84 parts by weight, dimethyl terephthalate (hereinafter sometimes abbreviated as DMT) 15.54 parts by weight, titanium tetrabutoxide 20.42 × 10 ^{− 3} parts by weight was placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under normal pressure of nitrogen atmosphere, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 40 kPa over 20 minutes, and the temperature was increased to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 0.13 kPa or less over 120 minutes, and the polymerization reaction was carried out with stirring for 1 hour under the conditions of 250 ° C. and 0.13 kPa or less. Thereafter, the produced polyester carbonate copolymer was extracted while pelletizing. The polyester carbonate had a specific viscosity of 0.196 and a pellet b value of 4.2.

(Synthesis 1-4) Resin B
Polyester carbonate pellets were obtained in the same manner as in Synthesis 1-3 except that BPEF-1 in Synthesis 1-3 was changed to BPEF-2. The polyester carbonate had a specific viscosity of 0.212 and a pellet b value of 10.3.

(Synthesis 1-5) Resin C
Using BPEF-1 and DPC, 30 parts by weight of BPEF, 2.5 parts by weight of BPA, 27 parts by weight of ethylene glycol, 38 parts by weight of DMT and 0.042 parts by weight of calcium acetate were placed in a reaction kettle equipped with a stirrer and a distiller and stirred. However, the ester exchange reaction was carried out by gradually heating from 190 ° C. to 230 ° C. according to a conventional method. After extracting a predetermined amount of methanol out of the system, 0.012 part by weight of germanium oxide as a polymerization catalyst and 0.033 part of trimethyl phosphate are added, and the temperature is gradually increased and the pressure is gradually reduced. While removing the glycol, the heating bath temperature was 280 ° C. and the degree of vacuum was 1 Torr or less. This condition was maintained, the increase in viscosity was waited, and the reaction was terminated after 2 hours. Thereafter, the produced polyester copolymer was extracted while pelletizing. The specific viscosity of the polyester was 0.190, and the pellet b value was 4.3.

(Synthesis 1-6) Resin C
Polyester pellets were obtained in the same manner as in Synthesis 1-5 except that BPEF-1 in Synthesis 1-5 was changed to BPEF-2. The polyester carbonate had a specific viscosity of 0.212 and a pellet b value of 10.1.

(Example 2)
(Melting test 2-1)
BPEF-1: 2.7 g and DPC 1.8 g were kept in the atmosphere at 270 ° C. for 30 minutes. The Hazen color number of the mixed melt was 150.
(Melting test 2-2)
BPEF-2: 2.7 g and DPC 1.8 g were kept in the atmosphere at 270 ° C. for 30 minutes. The Hazen color number of the mixed melt was 400.

(Example 3)
(Melting test 3-1)
BPEF-1: 3.0 g and DPC 1.5 g were held at 180 ° C. in the atmosphere for 270 minutes. The Hazen color number of the mixed melt was 100.
(Melting test 3-2)
BPEF-2: 3.0 g and DPC 1.5 g were held at 180 ° C. in the atmosphere for 270 minutes. The Hazen color number of the mixed melt was 300.

(Comparative Example 1)
(Melting test 4-1)
BPEF-1: 4.5 g was kept in the atmosphere at 270 ° C. for 30 minutes. The Hazen color number of the mixed melt was 200.
(Melting test 4-2)
BPEF-2: 4.5 g was kept in the atmosphere at 270 ° C. for 30 minutes. The Hazen color number of the mixed melt was 200.

(Comparative Example 2)
(Melting test 5-1)
BPEF-1: 2.3 g and 2.3 g of DPC were held in the atmosphere at 320 ° C. for 150 minutes. The Hazen color number of the mixed melt was 500.
(Melting test 5-2)
BPEF-2: 2.3 g and 2.3 g of DPC were held in the atmosphere at 320 ° C. for 150 minutes. The Hazen color number of the mixed melt was 500.

(Comparative Example 3)
(Melting test 6-1)
BPEF-1: 2.3 g and 2.3 g of DPC were kept in the atmosphere at 175 ° C. for 300 minutes. The Hazen color number of the mixed melt was 200.
(Melting test 6-2)
BPEF-2: 2.3 g and 2.3 g of DPC were kept in the atmosphere at 175 ° C. for 300 minutes. The Hazen color number of the mixed melt was 200.

(Comparative Example 4)
(Melting test 7-1)
BPEF-1: 2.3 g and 2.3 g of DPC were kept in the atmosphere at 260 ° C. for 180 minutes. The Hazen color number of the mixed melt was 500.
(Melting test 7-2)
BPEF-2: 2.3 g and 2.3 g of DPC were kept in the atmosphere at 260 ° C. for 180 minutes. The Hazen color number of the mixed melt was 500.

  From Table 1, in BPEF-1 and BPEF-2 of Examples 1-3, it is possible to determine whether the hue of the raw material is good or bad. On the other hand, in BPEF-1 and BPEF-2 of Comparative Examples 1 to 4, there is no difference in hue in the raw material, and it is impossible to determine whether the hue in the raw material is good or bad.

  According to the present invention, a thermoplastic resin useful for optical applications such as an optical lens, a prism, an optical disk substrate, and an optical film can be stably produced.

Claims (7)

Melting after holding a mixture of aliphatic terminal diol represented by general formula (I) and aromatic carbonic acid diester in a weight ratio of 3: 2 to 5: 1 in the molten state at 150 to 320 ° C. for 10 to 150 minutes in the air A method for testing the heat resistance of an aliphatic terminal diol represented by the general formula (I), wherein the hue is evaluated.

(In formula (I), R1 and R2 are each independently an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms, and R3 to R6 are each independently a hydrogen atom, an alkyl group, an alkoxyl group, and a cycloalkyl group. , Cycloalkoxyl group, aryl group or aryloxy group, A1 is a single bond, alkyl group, alkoxyl group, cycloalkyl group, cycloalkoxyl group, aryl group or aryloxy group.   The heat resistance test method according to claim 1, wherein A1 in the general formula (I) is a fluorene ring.   The heat resistance test method according to claim 1, wherein the general formula (I) is 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene.   The heat resistance test method according to any one of claims 1 to 3, wherein the aromatic carbonic acid diester is diphenyl carbonate. A method for producing a thermoplastic resin in which an aliphatic terminal diol represented by the general formula (I) is polymerized by heating and melting, and (A): the heat resistance test according to claim 1 is performed on the aliphatic terminal diol. Step (B): Based on the heat resistance test result obtained in the above step (A), a mixture of an aliphatic terminal diol and an aromatic carbonic acid diester in a weight ratio of 2: 1 was kept in the atmosphere at 270 ° C. for 30 minutes. Step (C) of selecting an aliphatic terminal diol having a molten APHA of 300 or less as a good product when converted to molten APHA: Melt polymerization is performed using the aliphatic terminal diol selected as a good product in the step (B). The manufacturing method of the thermoplastic resin characterized by passing through a process.   6. The method for producing a thermoplastic resin according to claim 5, wherein the aliphatic terminal diol is 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and diphenyl carbonate.   The production method according to any one of claims 5 to 6, wherein the thermoplastic resin is at least one selected from the group consisting of polycarbonate, polyester carbonate, and polyester.